Performance comparison of two newly developed bimetallic (X-Mo/Al2O3, X=Fe or Co) catalysts for reverse water gas shift reaction

The performance of the two newly developed bimetallic catalysts based on the precursor, Mo/Al_2O_3, was compared for reverse water gas shift(RWGS) reaction. The structures of the precursor and the catalysts were studied using X-ray diffraction(XRD), Brunauer–Emmett–Teller(BET) analysis, inductively coupled plasma-atomic emission spectrometry(ICP-AES), CO chemisorption, temperature programmed reduction of hydrogen(H_2-TPR) and scanning electron microscopy(SEM) techniques. The activity of Fe-Mo and Co-Mo catalysts was compared in a fixed bed reactor at different temperatures. It is shown that the Co-Mo catalyst has higher CO_2 conversion at all temperature level. The time-on-stream(TOS) analysis of the activity of catalysts for the RWGS reaction was carried out over a continuous period of 60h for both catalysts. The Fe-Mo/Al_2O_3 catalyst exhibits good stability within a period of 60h, however, the Co-Mo/Al_2O_3 is gradually deactivated after 50h of reaction time. Existence of(Fe_2(MoO4_))_3 phase in Fe-Mo/Al_2O_3 catalyst makes this catalyst more stable for RWGS reaction.     

Low-temperature CO2 hydrogenation to CO on Ni-incorporated LaCoO3 perovskite catalysts

This work introduces LaCo_1-xNi_xO₃ (x = 0, 0.1, 0.25, and 0.4) perovskite catalysts for enhancing the low temperature performance of reverse water-gas shift (RWGS) reaction. Incorporating Ni lowers the interaction between La-site and B-site, weakening the electron donation from La-site to B-site. The B-site elements with the weak interaction can be easily diffused from the bulk to form exsolved bimetallic Co–Ni alloy on the surface. This different interaction trends further control H₂ dissociation activity and CO desorption that affect CO₂ conversion and CO selectivity, respectively. While the Ni-incorporated catalyst shows a higher metal dispersion to enhance H₂ dissociation activity and increases CO₂ conversion, the La-sites with the weak electron donation further drive the strong adsorption of CO molecules to be additionally hydrogenated, eventually lower CO selectivity. However, incorporating 10 at% Ni into the B site of LaCoO₃ (LaCo_0.9Ni_0.1O₃) achieved a balanced effect between facile H₂ dissociation and CO desorption to maximize RWGS activity. The LaCo_0.9Ni_0.1O₃ catalyst displayed outstanding activity with an average CO₂ conversion of 30.8%, which is close to the equilibrium conversion, and a CO selectivity of 98.8% at 475 °C over 50 h.     

Supported mesoporous Cu/CeO2-δ catalyst for CO2 reverse water–gas shift reaction to syngas

The design and development of a high performance hydrogenation catalyst is an important challenge in the utilization of CO₂ as resources. The catalytic performances of the supported catalyst can be effectively improved through the interaction between the active components and the support materials. The obtained results demonstrated that the oxygen vacancies and active Cu⁰ species as active sites can be formed in the Cu/CeO_2-δ catalysts by the H₂ reduction at 400 °C. The synergistic effect of the surface oxygen vacancies and active Cu⁰ species, and Cu⁰–CeO_2-δ interface structure enhanced catalytic activity of the supported xCu/CeO_2-δ catalysts. The electronic effect between Cu and Ce species boosted the adsorption and activation performances of the reactant CO₂ and H₂ molecules on the corresponding Cu/CeO_2-δ catalyst. The Cu/CeO_2-δ catalyst with the Cu loading of 8.0 wt% exhibited the highest CO₂ conversion rate in the RWGS reaction, reaching 1.38 mmol·g_cat⁻¹ min⁻¹ at 400 °C. Its excellent catalytic performance in the RWGS reaction was related to the complete synergistic interaction between the active species via Ce³⁺-□-Cu⁰ (□: oxygen vacancy). The Cu/CeO_2-δ composite material is a superior catalyst for the RWGS reaction because of its high CO₂ conversion and 100% CO selectivity.     

Surface properties of Ca,Ti-doped CeO2 and their influence on the reverse water-gas shift reaction

CeO₂-based materials can be found in a variety of catalytic processes, including the reverse water-gas shift (RWGS) reaction. Nevertheless, the interaction of molecular gases with the surfaces of such materials is still not clear. Recently, some progress was reported on the incorporation of neodymium (Nd) and calcium (Ca) into ceria and their effect on H₂O and CO₂ adsorption. Titanium (Ti), which has a much smaller ionic radius, has the ability to change the interaction landscape, both as a co-dopant to Ca and as a sole dopant in the CeO₂ system. In this study, the interactions of environmental gases (i.e., water vapor and CO₂) on the surface of Ti-doped CeO₂ and Ca,Ti co-doped CeO₂ were investigated. Ti addition to CeO₂ was shown to decrease water vapor uptake by up to 25% all while maintaining similar heats of adsorption. In the case of CO₂ adsorption, Ti addition to CeO₂ had lowered the uptake by more than 50% as well as lowering the heat of adsorption. Co-doping with Ti and Ca showed small decrease in H₂O uptake accompanied with increased heat of adsorption. For CO₂, the changes to the uptake and energetics were small and did not indicate a specific trend. The RWGS catalytic performance showed improvement by the addition of Ti in certain levels. The relationship between the doping, surface properties, gas-surface interactions, and catalytic performance is discussed.     

Kinetic study of methane reforming with carbon dioxide over NiCeMgAl bimodal pore catalyst

The kinetic behavior of NiCeMgAl bimodal pore catalyst for methane reforming with CO₂ was investigated after the elimination of external and internal diffusion effects in a fixed‐bed reactor as a function of temperature and partial pressures of reactants and products. Increase in CO₂ partial pressure favors the consumptions of CH₄ and CO₂ but inhibits the formation of H₂ due to the existence of reverse water gas shift (RWGS) reaction. The reforming rate increased first and then reached a horizontal stage with the rise of CH₄ partial pressure. A Langmuir–Hinshelwood model was developed assuming that the carbon deposition is ignorable but the RWGS reaction is non‐ignorable and the removal of adsorbed carbon intermediate is the rate‐determining step. A nonlinear least‐square method was applied to solve the kinetic parameters. The derived kinetic expression fits the experimental data very well with a R² above 0.97, and also predicts the products flow rate satisfactorily. © 2016 American Institute of Chemical Engineers AIChE J, 63: 2019–2029, 2017     

Chemical recycling of carbon dioxide emissions from a cement plant into dimethyl ether,a case study of an integrated process in France using a Reverse Water Gas Shift (RWGS) step

Recycling of carbon dioxide (CO₂) and hydrogen (H₂) into liquid fuel technology has recently gained wide public interest since it is a potential pathway to increase the liquid fuel supply and to mitigate CO₂ emissions simultaneously.     

Modeling and optimization of hydrogenation of CO2: Estimation of kinetic parameters via Artificial Bee Colony (ABC) and Differential Evolution (DE) algorithms

Global warming, climate change, fossil fuel depletion and steep hikes in the price of environmentally friendly hydrocarbons motivate researchers to investigate CO₂ hydrogenation for hydrocarbons production. However, due to the reaction complexities and varieties of produced species, the process mechanism and subsequently estimation of the kinetic parameters have been controversial yet. Therefore, estimating the kinetic parameters using Artificial Bee Colony (ABC) and Differential Evolution (DE) optimization algorithms based on Langmuir-Hinshelwood-Hougen-Watson (LHHW) mechanism is proposed as a possible remedy to fulfil the requirements. To this end, a one-dimensional heterogeneous model comprising detailed reaction rates of reverse water gas shift (RWGS), Fisher-Tropsch (FT) reactions and direct hydrogenation (DH) of CO₂ is developed. It is observed that ABC exhibiting 6.3% error in predicting total hydrocarbons selectivity is superior to DE algorithm with 32.9% error. Therefore, the model employed the estimated kinetic parameters obtained via ABC algorithm, is exploited for products distribution analysis. Results reveal that maximum 73.21% hydrocarbons (C₁C₄) selectivity can be achieved at 573 K and 1 MPa with 0.85% error compared to the experimental value of 72.59%. Accordingly, the proposed model can be exploited as a powerful tool for evaluating and predicting the performance of CO₂ hydrogenation to hydrocarbons process.     

Catalytic syngas production from greenhouse gasses: Performance comparison of Ru-Al2O3 and Rh-CeO2 catalysts

In this work, 3% Ru-Al₂O₃ and 2% Rh-CeO₂ catalysts were synthesized and tested for CH₄-CO₂ reforming activity using either CO₂-rich or CO₂-lean model biogas feed. Low carbon deposition was observed on both catalysts, which negligibly influenced catalytic activity. Catalyst deactivation during temperature programmed reaction was observed only with Ru-Al₂O₃, which was caused by metallic cluster sintering. Both catalysts exhibited good stability during the 70 h exposure to undiluted equimolar CH₄/CO₂ gas stream at 750 °C. By varying residence time in the reactor during CH₄-CO₂ reforming, very similar quantities of H₂ were consumed for water formation. Reverse water-gas shift (RWGS) reaction occurred to a very similar extent either with low or high WHSV values over both catalysts, revealing that product gas mixture contained near RWGS equilibrium composition, confirming the dominance of WGS reaction and showing that shortening the contact time would actually decrease the H₂/CO ratio in the syngas produced by CH₄-CO₂ reforming, as long as RWGS is quasi equilibrated. H₂/CO molar ratio in the produced syngas can be increased either by operating at higher temperatures, or by using a feed stream with CH₄/CO₂ ratio well above 1.